Keto esters



Patented Jan. 16, 1945 rrso STATES PATENT OFFICE KETO ESTERS Albert M.Cliflord, Stow, Ohio, assignor to Wingfoot Corporation, Akron, Ohio, acorporation of Delaware No Drawing. Application May 19, 1942,

Serial No. 443,645

3 Claims.

This invention relates to alicyclic keto esters of acids of the acrylicseries. These esters may be prepared by the interaction of a metal saltof an acid of the acrylic acid series and a halogen-substituted ketone,a metal halide being split out.

For example, cyclohexanonyl methacrylate may thus be prepared from asodium acrylate and 2-chloro cyclohexanone in accordance with thefollowing equation:

Where X represents hydrogen or an alkyl or halogen radical. The otheresters described herein may be similarly prepared.

The acrylates which are reacted with halogensubstituted alicyclicketones to give the keto esters of this invention are those of thepoly-- merizable acrylic acids. The alpha alkyl substituted acrylicacids yield especially useful esters. Among suitable acids whose alkalimetal salts may be mentioned are acrylic acid, methacrylic acid,ethacrylic acid, itaconic acids (OHFC-GGOH mcooa I where R is hydrogenor a hydrocarbon substituent), cinnamic acid and alpha phenyl acrylicacid.

The method of preparing the new esters is illustrated by the followingexamples to which, however, the invention is not limited, the compoundsbeing included within the scope of the invention regardless of themethod of preparation. EXAMPLE 1 Cyclohexanonyl methacrylate To asolution of 88 parts of NaOH in 800 parts of water was added withcooling and stirring 200 parts of methyl methacrylate containing 2 partsof hydroquinone and 2 parts of N,N'-diphenyl para phenylene diamine. Themixture was refluxed gently for 2 /2 hourssolution being substantiallycomplete, following which distillation at 35 mm. pressure was conducteduntil there was collected 191 parts of distillate. containing thegreater portion of the methanol generated. To one and one-fifth mols ofthe resulting sodium.methacrylate there was added 158 .grams 1.2 mols2-chloro cyclohexanone with stirring over a -minute period. The mixturewas then heated at a gentle reflux for two hours. After standingovernight the organic layer was separated, dried over CaSOr anddistilled under reduced pressure. The main fraction boiled over a rangeof 45-60" C. at 5 mm. The distillate, however, polymerized very quickly,even at low temperature (5 0.). In addition to. the distillate, aconsiderable portion remained as a polymerized, non-distillable residue.

EXAMPLE 2 Methyl cyclohemanonyi methacrylote 1. The cyclohexanonyl andalkyl cyclohexanonyl esters of an acid selected from the groupconsisting of acrylic acid and alpha alkyl acrylic acids.

2. As a new material methyl cyclohexanonyl methacrylate.

3. Cyclohexanone ester of methacrylic acid.

ALBERT M. CLIFFORD.

